CN105642345A - Preparation method of hydrophobic hierarchical pore solid acid-alkali bifunctional catalyst - Google Patents
Preparation method of hydrophobic hierarchical pore solid acid-alkali bifunctional catalyst Download PDFInfo
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Abstract
The invention relates to a preparation method of a hydrophobic hierarchical pore solid acid-alkali bifunctional catalyst, and belongs to the technical field of environment functional material preparation. According to the preparation method, alkali-functionalized hydrophobic nano particles (S-NH2) and span80 are taken as the emulsifier to prepare stable pickering high internal phase emulsion, wherein the water phase comprises deionized water and potassium sulfate, the oil phase comprises divinyl benzene, 1-hexene, trihydroxymethyl propane trimethyl acrylate (TMPTMA), and 2,2'-azodiisobutyronitrile (AIBN), then through emulsion polymerization and sulfonation, the hydrophobic hierarchical pore solid acid-alkali bifunctional catalyst (PAPCs) is obtained, and the catalytic effect of the catalyst can be observed in the one-step conversion of cellulose to prepare 5-hydroxymethyl furfural.
Description
Technical field
The preparation method that the present invention relates to a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst, belongs to technical field of environment function material preparation.
Background technology
Along with people are worried to present situations such as global warming and non-renewable fossil material storage level minimizings year by year, development clean energy resource and Renewable resource such as industrial chemicals are increasingly paid attention to; Abundant renewable bioenergy is mainly derived from the photosynthesis of plant, and it can produce the multiple effect such as the energy and constant source as organic compound, and therefore it is that potential going replaces Fossil fuel; In numerous applications, the application that Efficient Conversion produces this aspect of high valuable chemicals is gone to have very important significance with edible composition non-in cellulose or biomass; Wherein, platform chemicals 5 hydroxymethyl furfural plays key player in biomass energy, because much useful acid can be become by effective method migration, for instance, levulic acid and very promising 2,5-dimethyl furan fuel; In the method preparing 5 hydroxymethyl furfural, for alleviating energy crisis, acid-catalyzed dehydration C6The carbohydrate of unit such as cellulose goes the method preparing 5 hydroxymethyl furfural to have and is widely applied prospect most; In acid catalyzed reaction system, owing to heterogeneous catalysis has the advantages such as low corrosion, high catalytic activity and recyclability, process be simple and environmentally friendly, it instead of gradually has corrosivity uniformly acid's catalyst traditionally than example hydrochloric acid, sulphuric acid, perchloric acid; Recently, scientific research person is prepared for various solid catalyst, and prepare 5 hydroxymethyl furfural with their catalysis fibre element, such as, blue hypodesmus prunus mume (sieb.) sieb.et zucc. (Lanzafame) etc. has been successfully prepared load Disulfatozirconic acid. mesoporous silicon (SBA-15) solid acid catalyst by hydro-thermal method, and this solid acid catalysis fibre element under the water environment of 190 DEG C obtains the 5 hydroxymethyl furfural of high yield; And, Water-In-Oil (W/O) pik woods High Internal Phase Emulsion template can be used to prepare the porosu solid acid with connecting hole and highly acid big borehole jack aperture, and change into 5 hydroxymethyl furfural for catalysis fibre element, meanwhile, overcome in mesoporous catalyst and there is the shortcoming that macromole (such as cellulose) hardly diffuses in hole;Based on above research, the productivity of 5 hydroxymethyl furfural still has very big room for promotion, therefore, improves 5 hydroxymethyl furfural yield and remains a very stern challenge.
In recent years, scientific research person is probing into how from C always6The carbohydrate of unit obtains the 5 hydroxymethyl furfural of high yield, recognizes that cellulose will through typical three step process to 5 hydroxymethyl furfural simultaneously; Namely acid catalysis cellulose degradation is to glucose, and base catalysis glucose isomerization is dewatered to 5 hydroxymethyl furfural to fructose and fructose under sour environment; Therefore, scientific research person reasonably designs according to the three-step approach of cellulose to 5 hydroxymethyl furfural and the solid acid catalyst that synthesizes prepares 5-hydroxyl bran aldehyde for catalysis fibre element; Such as, Wus etc. successfully synthesize and have soda acid bifunctional macrovoid mesoporous silicon dioxide nano particle, and prepare 5 hydroxymethyl furfural as catalyst catalysis fibre element in ionic liquid, find that the difunctional solid catalyst of soda acid can increase the productivity of 5 hydroxymethyl furfural simultaneously; Period, Xiao Fengshou seminar has successfully synthesized a series of solid bronsted lowry acids and bases bronsted lowry mesoporous solid catalyst with different wetting, and solid acid is used for catalysis fructose and cellulose together with solid base catalyst, obtains the 5 hydroxymethyl furfural of high yield; Visible, it has been found that to there is the bifunctional hydrophobic multi-stage porous solid catalyst of soda acid and can well improve the productivity of 5-Hydroxymethylfurfural, but preparation has soda acid bifunctional hydrophobic porous solid catalyst and remains a serious challenge.
At present, the nanoparticle of Catalyzed by Basic Functionalized stablize water in oil pik Lin Gaonei phase template and sulfonation process combine there is the bifunctional hydrophobic porous level solid catalyst of soda acid for preparing it is not yet reported that.
Summary of the invention
The present invention is by using the hydrophobic nano-particles (S-NH of Catalyzed by Basic Functionalized2) and Span 80(span80) it is used as emulsifying agent to prepare stable pik woods High Internal Phase Emulsion, wherein aqueous phase includes deionized water and potassium sulfate, oil phase includes divinylbenzene (DVB), 1-hexene, trimethylol-propane trimethacrylate (TMPTMA) and 2,2'-azodiisobutyronitrile (AIBN), it is then passed through emulsion polymerization and sulfonation process obtains a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst (PAPCs), inquired into its catalytic effect subsequently by the catalytic reaction of a step conversion cellulose generation 5 hydroxymethyl furfural.
The technical solution used in the present invention is:
The preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst, carries out as steps described below:
(1) synthesis of the hydrophobic nano-particles of Catalyzed by Basic Functionalized
Glycidyl methacrylate (GMA) and H2O joins in the there-necked flask of 250 milliliters, after inflated with nitrogen ten minutes, add styrene (St) and diethylbenzene (DVB) inside, it is then heated to 90 DEG C, it is charged with potassium peroxydisulfate again, stirs 1-1.5 hour with 600 ~ 800rpm, after high speed centrifugation, 40 ~ 50 DEG C of vacuum drying ovens dry 20 ~ 24 hours, obtains hydrophobic epoxy styrene granule (that is: S-GMA); Hydrophobic epoxy styrene granule and the mass percentage concentration ratio of preparation are the NH of 22% ~ 25%3��H2O mixes, and stirs 9 ~ 10 hours under the reflux condensation mode of 90 DEG C, after high speed centrifugation, dries 10 ~ 12 hours, obtain hydrophobic nano-particles (the called after S-NH of Catalyzed by Basic Functionalized in 40 ~ 50 DEG C of vacuum drying ovens2).
(2) preparation of hydrophobic multi-stage porous solid acid-base bifunctional catalyst
First, make the hydrophobic nano-particles of Catalyzed by Basic Functionalized, divinylbenzene (DVB), Span 80(span80), 1-hexene, trimethylol-propane trimethacrylate (TMPTMA) and azodiisobutyronitrile (AIBN) are mixed to form oil phase, then potassium sulfate is dissolved and form aqueous phase in deionized water, under mechanical stirring finally, aqueous phase is added dropwise in oil phase, after 5 ~ 10 minutes, the stable pik woods High Internal Phase Emulsion formed is placed in 65 ~ 70 DEG C of oil bath pans and keeps 10 ~ 12 hours carrying out thermal-initiated polymerization reaction, the polymer obtained uses acetone surname extraction 20 ~ 24 hours at 70 ~ 80 DEG C, subsequently in 70 ~ 80 DEG C of baking ovens after dry 10 ~ 12 hours, obtain high internal phase polymeric.
Preparing high internal phase polymeric and the concentrated sulphuric acid that mass percentage concentration is 98% at room temperature reacts 10 ~ 12 hours, then filter, clean repeatedly until sulphuric acid is cleaned with deionized water, last after 70 ~ 80 DEG C of oven dryings 10 ~ 12 hours, obtain hydrophobic multi-stage porous solid acid-base bifunctional catalyst (PAPCs).
Wherein the glycidyl methacrylate (GMA) described in step (1), H2The mass volume ratio of O, styrene (St), diethylbenzene (DVB) and potassium peroxydisulfate is 0.5 ~ 0.6:58 ~ 60:1.8 ~ 2.0:0.8 ~ 1.0:0.06 ~ 0.08(mL/mL/mL/mL/g).
Wherein the hydrophobic epoxy styrene granule of the preparation described in step (1) and mass percentage concentration are the NH of 22% ~ 25%3��H2O mass volume ratio is 0.4 ~ 0.5:9.0 ~ 10(g/mL)
Wherein the hydrophobic nano-particles of oil phase neutral and alkali functionalization described in step (2), divinylbenzene (DVB), Span 80(span80), 1-hexene, trimethylol-propane trimethacrylate (TMPTMA) and azodiisobutyronitrile (AIBN) the mass volume ratio of each monomer be 0.25 ~ 0.3:0.4 ~ 0.5:0.25 ~ 0.3:1.8 ~ 2.0:0.4 ~ 0.5:0.04 ~ 0.05 (g/mL/mL/mL/mL/g).
Wherein in the aqueous phase described in step (2), deionized water and potassium sulfate mass ratio are 16 ~ 16.8:0.07 ~ 0.08(g/g).
Wherein the volume ratio of the oil phase described in step (2) and aqueous phase is 2.6 ~ 3.0:16 ~ 16.8(mL/mL)
Wherein the high internal phase polymeric described in step (2) and the concentrated sulphuric acid mass volume ratio that mass percentage concentration is 98% are 0.9 ~ 1.0:25 ~ 30(g/mL).
The technological merit of the present invention: synthesized the hydrophobic nano-particles of Catalyzed by Basic Functionalized according to prior art, and carry out stable pik woods High Internal Phase Emulsion with it further and be successfully prepared hydrophobic multi-stage porous solid acid-base bifunctional catalyst (PAPCs); Pik woods High Internal Phase Emulsion template technology can prepare multilevel hole material, and the particle of present invention Catalyzed by Basic Functionalized has synthesized multi-functional multi-stage porous solid catalyst as stabilizer; Divinylbenzene and trimethylol-propane trimethacrylate can increase the degree of cross linking of oil phase as cross-linking agent; 1-hexene has polymerization single polymerization monomer function, it may have regulate the hydrophobic function of material; Soda acid amount can reach adjustability by changing the content of diethylbenzene and stable particle; Hydrophobicity and multi-stage porous can be determined according to the degree of cross linking of each monomer and 1-hexene amount; PAPCs can realize the simple and quick mixture from reaction and separate; PAPCs has the catalytic effect of brilliance simultaneously.
Accompanying drawing explanation
Fig. 1 be in embodiment 1 preparation S-GMA(a), S-NH2The water contact angle figure of (b) and PAPCs (c). As can be seen from the figure embodiment 1 obtains the water contact angle of S-GMA and is about 140 ��, finds out, S-NH from b2Water contact angle be about 121 ��, basic group-NH is described2Successfully having connected, alkalescence is successfully obtained, it can be seen that the water contact angle of PAPCs is 103 �� from c, illustrates that the catalyst obtained is hydrophobicity.
Fig. 2 be in embodiment 1 preparation S-GMA(a), S-NH2The scanning electron microscope (SEM) photograph of (b) and PAPCs (c). Finding out from a, it is 100 nanometers that embodiment 1 obtains S-GMA mean diameter; Finding out from b, embodiment 1 obtains S-NH2Mean diameter be 200 nanometers, further illustrate basic group-NH2Successfully it is connected on S-GMA granule and the success of nano-particle alkaline modification; Finding out from c, the PAPCs average pore size that embodiment 1 obtains is 20 microns, and the average pore size of connecting hole is 1 micron.Illustrate that PAPCs has hierarchical porous structure.
Fig. 3 is PAPCs (a), S-GMA(b in embodiment 1) and S-NH2Fourier-the infrared spectrogram of (c). In infrared spectrogram, 1033cm-1Corresponding is the peak of C S, 1162cm-1It is-SO3The absworption peak of H, 1456cm-1Corresponding is phenyl ring, but 1630cm-1That corresponding is-NH2Bending vibration; As can be seen from the figure the PAPCs sulfonation success of embodiment 1, and can be clearly seen that S-NH2There is obvious-NH2Absworption peak, this shows that amino is successfully connected on granule.
Fig. 4 is the nitrogen adsorption of PAPCs-desorption isotherm figure and graph of pore diameter distribution in embodiment 1; As can be seen from the figure, embodiment 1 obtains polymer P APCs and all shows typical IV type isothermal line and occur capillary condensation phenomenon in the relative pressure range of 0.1-0.9, these phenomenons all show that these materials all contain meso-hole structure, and pore size is about 10.7 nanometers simultaneously.
Fig. 5 be in embodiment 1 for PAPCs ammonia temperature programmed desorption figure (a) and carbon dioxide temperature programmed desorption figure (b); From a figure, can be seen that polymer P APCs shows weak, strong acid and super acids three types, from b figure, show weak, highly basic and super base three types simultaneously, and embodiment 1 obtains sour total amount and the alkali total amount respectively 17.32mmolg of PAPCs-1And 6.2mmolg-1��
Detailed description of the invention
The preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst described in technique scheme, and implement analyze particularly as follows:
After pretreatment at 0.1g cellulose and present 120 DEG C of 2.0g1-ethyl-3-methylimidazole chloride salt ions liquid 30 minutes, in reaction vessel, then add 40mgPAPCs catalyst, after reacting 1.0 hours. Next add in reactor with a small amount of deionized water, the browner volumetric flask constant volume with 100 milliliters, finally with the content of the 5 hydroxymethyl furfural of efficient liquid phase instrument analysis synthesis. Wherein n1(mol) it is analyze the mole of carbon atom, n in the 5 hydroxymethyl furfural obtained0(mol) for the integral molar quantity of institute's carbon atoms in untreated cellulose.
Below in conjunction with being embodied as example, the present invention will be further described.
Embodiment 1:
1, the preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst, it is characterised in that carry out as steps described below:
(1) synthesis of the hydrophobic nano-particles of Catalyzed by Basic Functionalized
H the glycidyl methacrylate (GMA) of 0.5mL and 59mL2O joins in the there-necked flask of 250 milliliters, after inflated with nitrogen ten minutes, add the styrene (St) of 1.8mL and the diethylbenzene (DVB) of 0.8mL inside, it is then heated to 90 DEG C, again toward the potassium peroxydisulfate of wherein 0.06g, stir 1-1.5 hour with 600 ~ 800rpm, after high speed centrifugation, 40 ~ 50 DEG C of vacuum drying ovens dry 20 ~ 24 hours, obtains hydrophobic epoxy styrene granule (that is: S-GMA); The hydrophobic epoxy styrene granule of 0.4g and the mass percentage concentration ratio of 9.0mL of preparation are the NH of 22% ~ 25%3��H2O mixes, and stirs 9 ~ 10 hours under the reflux condensation mode of 90 DEG C, after high speed centrifugation, dries 10 ~ 12 hours, obtain hydrophobic nano-particles (the called after S-NH of Catalyzed by Basic Functionalized in 40 ~ 50 DEG C of vacuum drying ovens2).
(2) preparation of hydrophobic multi-stage porous solid acid-base bifunctional catalyst
First, make the hydrophobic nano-particles of 0.25g Catalyzed by Basic Functionalized, 0.4mL divinylbenzene (DVB), 0.25mL Span 80(span80), 1.8mL1-hexene, 0.4mL trimethylol-propane trimethacrylate (TMPTMA) and 0.04g azodiisobutyronitrile (AIBN) are mixed to form 2.6mL oil phase, then 0.07g potassium sulfate is dissolved in 16mL deionized water and forms 16mL aqueous phase, under mechanical stirring finally, aqueous phase is added dropwise in oil phase, after 5 ~ 10 minutes, the stable pik woods High Internal Phase Emulsion formed is placed in 65 ~ 70 DEG C of oil bath pans and keeps 10 ~ 12 hours carrying out thermal-initiated polymerization reaction, the polymer obtained uses acetone surname extraction 20 ~ 24 hours at 70 ~ 80 DEG C, subsequently in 70 ~ 80 DEG C of baking ovens after dry 10 ~ 12 hours, obtain high internal phase polymeric.
Concentrated sulphuric acid high internal phase polymeric and 25mL98% mass percentage concentration ratio being prepared by 0.9g at room temperature reacts 10 ~ 12 hours, then filter, clean repeatedly until sulphuric acid is cleaned with deionized water, last after 70 ~ 80 DEG C of oven dryings 10 ~ 12 hours, obtain hydrophobic multi-stage porous solid acid-base bifunctional catalyst (PAPCs).
2, catalytic performance analysis test
After pretreatment at 0.1g cellulose and present 120 DEG C of 2.0g1-ethyl-3-methylimidazole chloride salt ions liquid 30 minutes, in reaction vessel, then add 40mgPAPCs catalyst, after reacting 1.0 hours. Next add in reactor with a small amount of deionized water, the browner volumetric flask constant volume with 100 milliliters, finally with the content of the 5 hydroxymethyl furfural of efficient liquid phase instrument analysis synthesis, and calculate the productivity of 5 hydroxymethyl furfural according to result.
Result shows: the productivity of the 5 hydroxymethyl furfural that PAPCs catalysis fibre element obtains is 30.5%.
3, the physicochemical property of material characterizes
(1) being prepared for the emulsion of water in oil pik Lin Gaonei phase, high internal phase polymeric and hydrophobic multi-stage porous solid acid-base bifunctional catalyst (PAPCs) respectively according to the method for example 1, result shows that the method can be prepared and has the multifunction catalyst that multi-stage porous, soda acid are difunctional, hydrophobic.
(2) test in example 1 S-GMA(a of preparation), S-NH2The water contact angle figure of (b) and PAPCs (c); As can be seen from Figure 1 embodiment 1 obtains the water contact angle of S-GMA and is about 140 ��, finds out, S-NH from b2Water contact angle be about 121 ��, basic group-NH is described2Successfully having connected, alkalescence is successfully obtained, it can be seen that the water contact angle of PAPCs is 103 �� from c, illustrates that the catalyst obtained is hydrophobicity.
(3) as in figure 2 it is shown, test in example 1 S-GMA(a of preparation), S-NH2The scanning electron microscope (SEM) photograph of (b) and PAPCs (c); Finding out from a, it is 100 nanometers that embodiment 1 obtains S-GMA mean diameter, finds out from b, and embodiment 1 obtains S-NH2Mean diameter be 200 nanometers, further illustrate basic group-NH2Successfully being connected on S-GMA granule and the success of nano-particle alkaline modification, find out from c, the PAPCs average pore size that embodiment 1 obtains is 20 microns, and the average pore size of connecting hole is 1 micron, illustrates that PAPCs has hierarchical porous structure.
(4) as it is shown on figure 3, test PAPCs (a), S-GMA(b in example 1) and S-NH2Fourier-the infrared spectrogram of (c); In infrared spectrogram, 1033cm-1Corresponding is the peak of C S, 1162cm-1It is-SO3The absworption peak of H, 1456cm-1Corresponding is phenyl ring, but 1630cm-1That corresponding is-NH2Bending vibration; As can be seen from the figure the PAPCs sulfonation success of embodiment 1, and can be clearly seen that S-NH2There is obvious-NH2Absworption peak, this shows that amino is successfully connected on granule.
(5) nitrogen adsorption of PAPCs-desorption isotherm figure and graph of pore diameter distribution in example 1 are tested; All showing typical IV type isothermal line figure 4, it is seen that embodiment 1 obtains polymer P APCs and occur capillary condensation phenomenon in the relative pressure range of 0.1-0.9, these phenomenons all show that these materials all contain meso-hole structure. Pore size is about 10.7 nanometers simultaneously.
(6) as it is shown in figure 5, test in example 1 for PAPCs ammonia temperature programmed desorption figure (a) and carbon dioxide temperature programmed desorption figure (b); From a figure, can be seen that polymer P APCs shows weak, strong acid and super acids three types;From b figure, show weak, highly basic and super base three types simultaneously, and embodiment 1 obtains sour total amount and the alkali total amount respectively 17.32mmolg of PAPCs-1And 6.2mmolg-1��
Embodiment 2:
1, the preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst, it is characterised in that carry out as steps described below:
(1) synthesis of the hydrophobic nano-particles of Catalyzed by Basic Functionalized
According to prior art, the H of the glycidyl methacrylate (GMA) of 0.6mL and 60mL2O joins in the there-necked flask of 250 milliliters, after inflated with nitrogen ten minutes, add the styrene (St) of 2.0mL and the diethylbenzene (DVB) of 1.0mL inside, it is then heated to 90 DEG C, again toward the potassium peroxydisulfate of wherein 0.08g, stir 1-1.5 hour with 600 ~ 800rpm, after high speed centrifugation, 40 ~ 50 DEG C of vacuum drying ovens dry 20 ~ 24 hours, obtains hydrophobic epoxy styrene granule (that is: S-GMA); The hydrophobic epoxy styrene granule of 0.5g and the mass percentage concentration ratio of 10mL of preparation are the NH of 22% ~ 25%3��H2O mixes, and stirs 9 ~ 10 hours under the reflux condensation mode of 90 DEG C, after high speed centrifugation, dries 10 ~ 12 hours, obtain hydrophobic nano-particles (the called after S-NH of Catalyzed by Basic Functionalized in 40 ~ 50 DEG C of vacuum drying ovens2).
(2) preparation of hydrophobic multi-stage porous solid acid-base bifunctional catalyst
First, make the hydrophobic nano-particles of 0.3g Catalyzed by Basic Functionalized, 0.5mL divinylbenzene (DVB), 0.3mL Span 80(span80), 2.0mL1-hexene, 0.5mL trimethylol-propane trimethacrylate (TMPTMA) and 0.05g azodiisobutyronitrile (AIBN) are mixed to form 3.0mL oil phase, then 0.08g potassium sulfate is dissolved in 16.8mL deionized water and forms 16.8mL aqueous phase, under mechanical stirring finally, aqueous phase is added dropwise in oil phase, after 5 ~ 10 minutes, the stable pik woods High Internal Phase Emulsion formed is placed in 65 ~ 70 DEG C of oil bath pans and keeps 10 ~ 12 hours carrying out thermal-initiated polymerization reaction, the polymer obtained uses acetone surname extraction 20 ~ 24 hours at 70 ~ 80 DEG C, subsequently in 70 ~ 80 DEG C of baking ovens after dry 10 ~ 12 hours, obtains high internal phase polymeric.
Concentrated sulphuric acid high internal phase polymeric and 30mL98% mass ratio being prepared by 1.0g at room temperature reacts 10 ~ 12 hours, then filter, clean repeatedly until sulphuric acid is cleaned with deionized water, last after 70 ~ 80 DEG C of oven dryings 10 ~ 12 hours, obtain hydrophobic multi-stage porous solid acid-base bifunctional catalyst (PAPCs).
2, catalytic performance analysis test
After pretreatment at 0.1g cellulose and present 120 DEG C of 2.0g1-ethyl-3-methylimidazole chloride salt ions liquid 30 minutes, in reaction vessel, then add 40mgPAPCs catalyst, after reacting 1.0 hours. Next add in reactor with a small amount of deionized water, the browner volumetric flask constant volume with 100 milliliters, finally with the content of the 5 hydroxymethyl furfural of efficient liquid phase instrument analysis synthesis, and calculate the productivity of 5 hydroxymethyl furfural according to result.
Result shows: the productivity of the 5 hydroxymethyl furfural that PAPCs catalysis fibre element obtains is 30.3%.
Embodiment 3:
1, the preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst, it is characterised in that carry out as steps described below:
(1) synthesis of the hydrophobic nano-particles of Catalyzed by Basic Functionalized
H the glycidyl methacrylate (GMA) of 0.55mL and 58mL2O joins in the there-necked flask of 250 milliliters, after inflated with nitrogen ten minutes, add the styrene (St) of 1.9mL and the diethylbenzene (DVB) of 0.9mL inside, it is then heated to 90 DEG C, again toward the potassium peroxydisulfate of wherein 0.07g, stir 1-1.5 hour with 600 ~ 800rpm, after high speed centrifugation, 40 ~ 50 DEG C of vacuum drying ovens dry 20 ~ 24 hours, obtains hydrophobic epoxy styrene granule (that is: S-GMA);The hydrophobic epoxy styrene granule of 0.45g and the mass percentage concentration ratio of 9.5mL of preparation are the NH of 22% ~ 25%3��H2O mixes, and stirs 9 ~ 10 hours under the reflux condensation mode of 90 DEG C, after high speed centrifugation, dries 10 ~ 12 hours, obtain hydrophobic nano-particles (the called after S-NH of Catalyzed by Basic Functionalized in 40 ~ 50 DEG C of vacuum drying ovens2).
(2) preparation of hydrophobic multi-stage porous solid acid-base bifunctional catalyst
First, make the hydrophobic nano-particles of 0.27g Catalyzed by Basic Functionalized, 0.45mL divinylbenzene (DVB), 0.27mL Span 80(span80), 1.9mL1-hexene, 0.45mL trimethylol-propane trimethacrylate (TMPTMA) and 0.045g azodiisobutyronitrile (AIBN) are mixed to form 2.8mL oil phase, then 0.075g potassium sulfate is dissolved in 16.4mL deionized water and forms 16.4mL aqueous phase, under mechanical stirring finally, aqueous phase is added dropwise in oil phase, after 5 ~ 10 minutes, the stable pik woods High Internal Phase Emulsion formed is placed in 65 ~ 70 DEG C of oil bath pans and keeps 10 ~ 12 hours carrying out thermal-initiated polymerization reaction, the polymer obtained uses acetone surname extraction 20 ~ 24 hours at 70 ~ 80 DEG C, subsequently in 70 ~ 80 DEG C of baking ovens after dry 10 ~ 12 hours, obtains high internal phase polymeric.
Concentrated sulphuric acid high internal phase polymeric and 27mL98% mass ratio being prepared by 0.95g at room temperature reacts 10 ~ 12 hours, then filter, clean repeatedly until sulphuric acid is cleaned with deionized water, last after 70 ~ 80 DEG C of oven dryings 10 ~ 12 hours, obtain hydrophobic multi-stage porous solid acid-base bifunctional catalyst (PAPCs).
2, catalytic performance analysis test
After pretreatment at 0.1g cellulose and present 120 DEG C of 2.0g1-ethyl-3-methylimidazole chloride salt ions liquid 30 minutes, in reaction vessel, then add 40mgPAPCs catalyst, after reacting 1.0 hours. Next add in reactor with a small amount of deionized water, the browner volumetric flask constant volume with 100 milliliters, finally with the content of the 5 hydroxymethyl furfural of efficient liquid phase instrument analysis synthesis, and calculate the productivity of 5 hydroxymethyl furfural according to result.
Result shows: the productivity of the 5 hydroxymethyl furfural that PAPCs catalysis fibre element obtains is 30.1%.
Claims (8)
1. the preparation method of a hydrophobic multi-stage porous solid acid-base bifunctional catalyst, it is characterised in that: carry out as steps described below:
First, make the hydrophobic nano-particles of Catalyzed by Basic Functionalized, divinylbenzene (DVB), Span 80(span80), 1-hexene, trimethylol-propane trimethacrylate (TMPTMA) and azodiisobutyronitrile (AIBN) are mixed to form oil phase, then potassium sulfate is dissolved and form aqueous phase in deionized water, under mechanical stirring finally, aqueous phase is added dropwise in oil phase, after 5 ~ 10 minutes, the stable pik woods High Internal Phase Emulsion formed is placed in 65 ~ 70 DEG C of oil bath pans and keeps 10 ~ 12 hours carrying out thermal-initiated polymerization reaction, the polymer obtained uses acetone surname extraction 20 ~ 24 hours at 70 ~ 80 DEG C, subsequently in 70 ~ 80 DEG C of baking ovens after dry 10 ~ 12 hours, obtain high internal phase polymeric,
Preparing high internal phase polymeric and the concentrated sulphuric acid that mass percentage concentration is 98% at room temperature reacts 10 ~ 12 hours, then filter, clean repeatedly until sulphuric acid is cleaned with deionized water, last after 70 ~ 80 DEG C of oven dryings 10 ~ 12 hours, obtain hydrophobic multi-stage porous solid acid-base bifunctional catalyst (PAPCs).
2. the preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst as claimed in claim 1, it is characterised in that the synthetic method of the hydrophobic nano-particles of Catalyzed by Basic Functionalized is as follows:
Glycidyl methacrylate (GMA) and H2O joins in the there-necked flask of 250 milliliters, after inflated with nitrogen ten minutes, add styrene (St) and diethylbenzene (DVB) inside, it is then heated to 90 DEG C, it is charged with potassium peroxydisulfate again, stirs 1-1.5 hour with 600 ~ 800rpm, after high speed centrifugation, 40 ~ 50 DEG C of vacuum drying ovens dry 20 ~ 24 hours, obtains hydrophobic epoxy styrene granule (that is: S-GMA);Hydrophobic epoxy styrene granule and the mass percentage concentration ratio of preparation are the NH of 22% ~ 25%3��H2O mixes, and stirs 9 ~ 10 hours under the reflux condensation mode of 90 DEG C, after high speed centrifugation, dries 10 ~ 12 hours, obtain hydrophobic nano-particles (the called after S-NH of Catalyzed by Basic Functionalized in 40 ~ 50 DEG C of vacuum drying ovens2).
3. the preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst as claimed in claim 2, it is characterised in that: described glycidyl methacrylate (GMA), H2The mass volume ratio of O, styrene (St), diethylbenzene (DVB) and potassium peroxydisulfate is 0.5 ~ 0.6:58 ~ 60:1.8 ~ 2.0:0.8 ~ 1.0:0.06 ~ 0.08(mL/mL/mL/mL/g).
4. the preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst as claimed in claim 2, it is characterised in that: the hydrophobic epoxy styrene granule of described preparation and mass percentage concentration are the NH of 22% ~ 25%3��H2O mass volume ratio is 0.4 ~ 0.5:9.0 ~ 10(g/mL).
5. the preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst as claimed in claim 1, it is characterised in that: the described hydrophobic nano-particles of oil phase neutral and alkali functionalization, divinylbenzene (DVB), Span 80(span80), 1-hexene, trimethylol-propane trimethacrylate (TMPTMA) and azodiisobutyronitrile (AIBN) the mass volume ratio of each monomer be 0.25 ~ 0.3:0.4 ~ 0.5:0.25 ~ 0.3:1.8 ~ 2.0:0.4 ~ 0.5:0.04 ~ 0.05 (g/mL/mL/mL/mL/g).
6. the preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst as claimed in claim 1, it is characterised in that: in described aqueous phase, deionized water and potassium sulfate mass ratio are 16 ~ 16.8:0.07 ~ 0.08(g/g).
7. the preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst as claimed in claim 1, it is characterised in that: described oil phase and the volume ratio of aqueous phase are 2.6 ~ 3.0:16 ~ 16.8(mL/mL).
8. the preparation method of a kind of hydrophobic multi-stage porous solid acid-base bifunctional catalyst as claimed in claim 1, it is characterised in that: described high internal phase polymeric and the concentrated sulphuric acid mass volume ratio that mass percentage concentration is 98% are 0.9 ~ 1.0:25 ~ 30(g/mL).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510157361.1A CN105642345B (en) | 2015-04-03 | 2015-04-03 | A kind of preparation method of hydrophobic multi-stage porous solid acid-base bifunctional catalyst |
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| CN106215969A (en) * | 2016-07-25 | 2016-12-14 | 江苏大学 | A kind of cerium dopping solid super acid catalyst and preparation method thereof |
| CN109395779A (en) * | 2018-09-21 | 2019-03-01 | 江苏大学 | A kind of preparation method and purposes of the multifunctional solid catalyst based on emulsion template method |
| CN110368987A (en) * | 2019-07-23 | 2019-10-25 | 华侨大学 | A kind of preparation method and applications of tree-shaped luffa solid-loaded ionic-liquid type catalyst |
| CN111566130A (en) * | 2018-01-05 | 2020-08-21 | 凸版印刷株式会社 | Composite particle, method for producing composite particle, dry powder, and resin composition for molding |
| CN114832837A (en) * | 2022-05-31 | 2022-08-02 | 南京林业大学 | Application of hydrophobically modified solid acid catalyst in cellulose acetate acetylation reaction |
| US12075775B2 (en) | 2018-04-27 | 2024-09-03 | Toppan Printing Co., Ltd. | Sustained-release composite particles, method for producing sustained-release composite particles, dry powder, and wallpaper |
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| CN106215969A (en) * | 2016-07-25 | 2016-12-14 | 江苏大学 | A kind of cerium dopping solid super acid catalyst and preparation method thereof |
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| CN111566130A (en) * | 2018-01-05 | 2020-08-21 | 凸版印刷株式会社 | Composite particle, method for producing composite particle, dry powder, and resin composition for molding |
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| US11685799B2 (en) | 2018-01-05 | 2023-06-27 | Toppan Printing Co., Ltd. | Composite particles, method of producing composite particles, dry powder, and molding resin composition |
| US12075775B2 (en) | 2018-04-27 | 2024-09-03 | Toppan Printing Co., Ltd. | Sustained-release composite particles, method for producing sustained-release composite particles, dry powder, and wallpaper |
| CN109395779A (en) * | 2018-09-21 | 2019-03-01 | 江苏大学 | A kind of preparation method and purposes of the multifunctional solid catalyst based on emulsion template method |
| CN110368987A (en) * | 2019-07-23 | 2019-10-25 | 华侨大学 | A kind of preparation method and applications of tree-shaped luffa solid-loaded ionic-liquid type catalyst |
| CN110368987B (en) * | 2019-07-23 | 2021-12-31 | 华侨大学 | Preparation method and application of tree-like loofah sponge supported ionic liquid catalyst |
| CN114832837A (en) * | 2022-05-31 | 2022-08-02 | 南京林业大学 | Application of hydrophobically modified solid acid catalyst in cellulose acetate acetylation reaction |
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